pH dependent reactions of cyclohexaamylose with carboxylic acids and anions are investigated by means of electrolytic conductance, pH potentiometry and acid-base spectrophotometry. The structures of resultant binary and ternary complexes are correlated in several series of substrates, among which are para-substituted cinnamic acids, in order to gain fundamental understanding of binding modes and driving forces in a system thought to model biological complexations.